Paper enhancing compositions, uses thereof and enhanced paper

ABSTRACT

The present invention provides certain paper enhancing compositions, typically aqueous compositions, for use in the manufacture and coating of paper, and paper products. The paper enhancing compositions provide certain paper processing advantages and distinct final paper product characteristics. The present invention further provides carbonate enhancing composition useful for preparing enhanced carbonate compositions used in the paper manufacturing processes.

CROSS-REFERENCE TO RELATED APPLICATIONS

The presently disclosed subject matter is related to U.S. patentapplication Ser. No. 16/745,846 entitled “Plastic Modifying Compositionsand Enhanced Carbonate Compositions” filed on Jan. 17, 2020; the entiredisclosure of which is incorporated herein by reference.

BACKGROUND

The present invention relates to paper enhancing compositions useful forthe manufacture of paper, paper products, paperboard and paperboardproducts, and coated paper and paperboard and products made therefromincluding, for example and without limitation, cardboard and cardboardproducts. Also provided are enhanced carbonate compositions comprisingat least one carbonate and at least one carbonate enhancing composition.

Although large-scale pulp-based paper processing methods have beenestablished since the 1840's, a variety of substrates have been used andcontinue being used over the millennia including, for example andwithout limitation, cotton, silk, bamboo, Phragmites (e.g., commonreeds) and traditional hard and soft wood sources. The use of suchsubstrates each have particular challenges and techniques, and eachtypically use one or more fillers that extend the use of substrate(s),frequently reducing cost of the final product, while imparting specificand desired properties to the final product. Process development,particularly processes for continued cost reduction while maintainingand improving desired and/or new qualities to the final paper productscontinue. Accordingly, the present disclosure provides certain aspectsrelative to such continued development and improvement of a variety ofproducts and processes for the processing of coated and uncoated paperand the coating of paper.

As further reviewed herein, once paper is manufactured, additionalchallenges exist when coating paper for a variety of uses. As such, thepresent invention also provides various aspects related to compositionsand methods related to the preparation and processing of paper and paperproducts post manufacture of paper including, for example, a variety ofcoatings for various purposes.

SUMMARY

One aspect of the present invention provides a paper forming mixturecomprising a paper making fiber and at least one carbonate enhancedcomposition of the present invention. Addition of such carbonateenhanced mixture is typically, without limitation, added to the papermaking process at the wet-end.

Further provided is a paper forming mixture comprising a pulp-basedmixture of pulp and at least one carbonate enhanced composition of thepresent invention.

An additional aspect of the present invention provides a paper formingmixture comprising a pulp-based mixture of pulp and at least onecarbonate enhanced composition of the present invention, wherein theamount of calcium carbonate filler is at least five percent (5%) greaterthan the amount calcium carbonate fill typically added to a given papertype. For example, and without limitation, as reviewed in part above,for a paper type typically using 10-30% fill, the amount of fill thatcan be added to the paper forming wet mixture will equal at least 31.5%of the total wet mixture. This increase in calcium carbonate fill amountcan be used for any paper type well known to the skilled artisan.

A further aspect of the present invention provides for a method ofmodifying the zeta potential of calcium carbonate used in a paper makingprocess comprising the addition of at least one carbonate enhancedcomposition of the present invention to the wet-end of a paper makingprocess. As used relative to the zeta potential, such modification canbe an increase or decrease of the zeta potential, but typically is anincrease in the zeta potential as used herein.

More particularly, the present invention also provides a method ofmodifying the zeta potential of calcium carbonate used in a pulp-basedpaper making process comprising the addition of at least one carbonateenhanced composition of the present invention to the wet-end of a papermaking process.

An additional aspect of the present invention provides for antimicrobialpaper, having a multitude of uses, comprising paper prepared by theaddition of at least one carbonate enhanced composition of the presentinvention to the wet-end of a paper making process. As used herein, theterm “antimicrobial activity” means the inhibition of microbes.

The present invention further provides a paper enhancing compositioncomprising water, at least one solubility enhancing aqueous composition,sodium hydroxide, copper sulfate and, optionally, at least onesurfactant selected from the group consisting of non-ionic surfactantsand/or anionic surfactants.

An additional aspect of the present invention provides an aqueous or,substantially aqueous, paper enhancing composition (aqueousnotwithstanding the potential for copper sulfate to not have completelydissolved in the paper enhancing composition) comprising an aqueousphase comprising a solubility enhancing aqueous composition wherein 1part of a first solution is added to about 15 to about 20 parts ofwater, frequently deionized water, to form a second solution; sodiumhydroxide solution having a concentration of about 5% to about 7.5%volume/volume of the total aqueous phase volume of the composition; atleast one surfactant selected from the group consisting of non-ionicsurfactants and anionic surfactants having a concentration from about0.05 percent to about 0.15 percent volume/volume of the total aqueousphase volume of the composition; and copper sulfate having aconcentration from about 20 percent to about 26 percent mass/volume ofthe total aqueous phase volume of the composition. As used herein, theterm “aqueous paper enhancing composition” also includes any suchcomposition that is substantially aqueous as indicated herein.

A further aspect of the present invention further comprises the additionof an acid or base to adjust the pH to a pH from about 2.5 to about 3.5to a paper enhancing composition of the present invention.

The present invention further provides a method of increasing at leastone of paper tensile strength, bond strength and burst strength comparedto paper prepared without the addition of at least one paper enhancingcomposition comprising the addition of at least one paper enhancingcomposition to the wet-end of the paper making process.

Another aspect of the present invention provides a method for decreasingthe interstitial pore size between and among paper fibers in awet-end-paper making process compared to paper prepared without theaddition of at least one paper enhancing composition comprising theaddition of at least one paper enhancing composition to the wet-end ofthe paper making process.

An additional aspect of the present invention provides a method forincreasing paper density compared to paper prepared without the additionof at least one paper enhancing composition comprising the addition ofat least one paper enhancing composition to the wet-end of the papermaking process.

A further aspect of the present invention provides for paper havingantimicrobial properties comprising paper prepared using at least onepaper enhancing composition during the wet-end process stage of papermaking.

Also provided herein is a method of modifying the zeta potential ofcalcium carbonate when used in the paper making process comprisingapplying at least one aqueous paper enhancing composition during thewet-end stage of paper production.

Further provided is a method of modifying the zeta potential of calciumcarbonate when used in a pulp-based paper making process comprisingapplying at least one aqueous paper enhancing composition during thewet-end stage of paper production.

Another aspect of the present invention provides for enhanced papercomprising paper having applied during the wet press stage of paperproduction at least one aqueous enhancing paper composition.

Further provided herein are the following methods:

-   -   A method of enhancing paper comprising applying at least one        aqueous paper enhancing composition during the wet press stage        of paper production.    -   A method of increasing at least one of the group consisting of        tensile strength, bond strength and burst strength in paper        compared to the respective tensile strength, bond strength and        burst strength of paper untreated with an aqueous paper        enhancing composition comprising applying at least one aqueous        paper enhancing composition during the wet press stage of paper        production.    -   A method of modifying the zeta potential of calcium carbonate        when used in the paper making process comprising applying at        least one aqueous paper enhancing composition during the wet        press stage of paper production.    -   More particularly, the present invention also provides a method        of modifying the zeta potential of calcium carbonate used in a        pulp-based paper making process comprising applying at least one        aqueous paper enhancing composition during the wet press stage        of paper production.    -   A method of increasing at least one of the group consisting of        paper tensile strength, bond strength and burst strength of        paper comprising applying at least one aqueous paper enhancing        composition during the wet press stage of paper production        compared to paper untreated with an aqueous paper enhancing        composition without an increase in caliper pose.

Further provided is antimicrobial paper, having a multitude of uses,comprising paper prepared by the application of at least one aqueouspaper enhancing composition of the present invention during the wetpress stage of paper production.

Another aspect of the present invention provides for a paper coatingcomprising at least one aqueous paper enhancing composition.

An additional aspect provides for paper coated with at least one aqueouspaper enhancing composition.

Another aspect of the present invention provides a method of increasingat least one of the group consisting of paper tensile strength, bondstrength and burst strength of paper comprising the application of acoating to paper comprising at least one paper enhancing composition ofthe present invention.

An additional aspect of the present invention provides for a method ofproviding at least one of protection from fingerprints and otherblemishes, help prevent metallic inks from tarnishing, and provide papersurfaces that can be written on with multiple media (including, withoutlimitation, pencil, pen, ink jet printers, laser jet printers off-setprinters and the like) comprising the application of a coating to papercomprising at least one paper enhancing composition of the presentinvention.

A further aspect of the present invention provides for a method ofproviding improvement of at least one of protection from fingerprintsand other blemishes, help prevent metallic inks from tarnishing, andprovide paper surfaces that can be written on with multiple media(including, without limitation, pencil, pen, ink jet printers, laser jetprinters off-set printers and the like) compared to paper coatings notincluding the application of at least one aqueous paper enhancingcomposition of the present invention comprising the application of acoating to paper comprising at least one paper enhancing composition ofthe present invention.

Accordingly, another aspect of the present invention provides for coatedpaper having antimicrobial activity comprising paper coated with atleast one aqueous paper enhancing composition of the present invention.

An additional aspect of the present invention provides for paper havingantimicrobial properties comprising paper coated with at least oneaqueous paper enhancing composition of the present invention.

Another aspect of the present invention provides for a method ofpreparing paper having antimicrobial activity comprising applying as acoating to paper at least one aqueous paper enhancing composition of thepresent invention to said paper.

Further provided is antimicrobial paper, having a multitude of uses,comprising paper prepared by the application of a coating of at leastone aqueous paper enhancing composition of the present invention duringthe wet press stage of paper production.

Another aspect of the present invention provides a method of extendingthe shelf-life of perishable foodstuff comprising placing such foodstuffin contact with paper coated with at least one aqueous paper enhancingcomposition of the present invention. Such shelf-life can be extendedfor at least 24 hours, providing substantial value to providers of suchperishable foodstuff.

Further provided is a method for preparing paper for medical andindustrial protective uses comprising applying as a coating to paper atleast one aqueous paper enhancing composition.

An additional aspect provides a method of preparing paper for use inmasks for mammalian, particularly human, use comprising applying as acoating at least one aqueous paper enhancing composition.

An additional aspect of the present invention provides a carbonateenhanced composition comprising at least one carbonate and at least onecarbonate enhancing composition.

Other aspects of the present invention provide a variety of methods ofusing a carbonate enhanced composition of the present invention to avariety of intermediate and final products as further described hereinbelow.

An additional aspect of the present invention provides a carbonateenhancing composition comprising an aqueous phase comprising asolubility enhancing aqueous composition wherein 1 part of a firstsolution is added to about 15 to about 20 parts of water to form asecond solution; sodium hydroxide solution having a concentration ofabout 5% to about 7.5% volume/volume of the total aqueous phase volumeof the composition; at least one surfactant selected from the groupconsisting of non-ionic surfactants and anionic surfactants having aconcentration from about 0.05 percent to about 0.15 percentvolume/volume of the total aqueous phase volume of the composition; andcopper sulfate having a concentration from about 20 percent to about 26percent mass/volume of the total aqueous phase volume of thecomposition; optionally comprising the addition of at least one acid orat least one base to adjust the final composition pH to a pH of about2.5 to about 3.5.

Another aspect of the present invention provides a carbonate enhancingcomposition comprising an aqueous phase comprising a solubilityenhancing aqueous composition wherein 1 part of a first solution isadded to about 15 to about 20 parts of water to form a second solutionand sodium hydroxide solution having a concentration of about 5% toabout 7.5% volume/volume of the total aqueous phase volume of thecomposition; and copper sulfate having a concentration from about 20percent to about 26 percent mass/volume of the total aqueous phasevolume of the composition, optionally comprising the addition of atleast one acid or at least one base to adjust the final composition pHto a pH of about 2.5 to about 3.5.

An additional aspect of the present invention provides an antimicrobialcomposition comprising at least one composition selected from the groupconsisting of at least one carbonate enhanced composition and at leastone carbonate enhancing composition, wherein the carbonate enhancingcomposition is optionally aqueous or substantially aqueous.

A further aspect of the present invention provides a product requiringat least one carbonate as an element in the manufacture thereofcomprising at least, in part, at least one carbonate enhancedcomposition used in the manufacture of such product.

An additional aspect of the present invention provides an antimicrobialcomposition comprising at least one carbonate enhanced composition.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of the present invention will be more fully appreciated byreference to the following detailed description when taken inconjunction with the following drawings in which:

FIG. 1. depicts a low resolution spectrogram with 1 part reaction unitto 5 parts total.

FIG. 2. depicts a high resolution spectrogram with 1 part reaction unitto 5 parts total.

FIG. 3. depicts a low resolution spectrogram with 1 part reaction unitto 10 parts total.

FIG. 4. depicts a high resolution spectrogram with 1 part reaction unitto 10 parts total.

FIG. 5. depicts a low resolution spectrogram with 1 part reaction unitto 20 parts total.

FIG. 6. depicts a high resolution spectrogram with 1 part reaction unitto 20 parts total.

Each of the spectrograms was run according to the respective teachingsof Example 6. Each of the spectrograms depicts compositions that arefree of salt crystals or other solids formed from the ammonium sulfateand sulfuric acid reactants.

While the aspects of the present disclosure are susceptible to variousmodifications and alternative forms, specific embodiments thereof areshown by way of example in the drawings and will herein be described indetail. It should be understood, however, that the drawings and detaileddescription are not intended to limit the disclosure to the particularforms illustrated but, on the contrary, the intention is to cover allmodifications, equivalents and alternatives falling within the spiritand scope of the present disclosure as defined by the appended claims.The headings used herein are used for organizational purposes only andare not meant to limit the scope of the description. As used throughoutthis application, the word “may” is used in a permissive sense, meaning:“having the potential to”; rather than the mandatory sense meaning:“must”. Similarly, the words “include”, “including” and “includes” meansincluding, without limitation. Additionally, as used in thisspecification and the appended claims, the singular forms “a’, “an” and“the” include singular and plural referents unless the content clearlydictates otherwise.

The scope of the present disclosure includes any feature or combinationof features disclosed herein (either explicitly or implicitly), or anygeneralization thereof, whether or not it mitigates any or all of theproblems addressed herein. Accordingly, new claims may be formulatedduring prosecution of this application (or an application claimingpriority thereto) to any such combinations of features. In particular,with reference to the appended claims, features from dependent claimsmay be combined with those of independent claims and features fromrespective independent claims may be combined in any appropriate mannerand not merely in the specific combinations enumerated in the appendedclaims.

DETAILED DESCRIPTION Definitions

The term “antimicrobial” means antibacterial, anti-fungal, antiviral andanti-mold, each individually and collectively.

The term “alkali and alkaline metal carbonates” have their traditionalmeanings in the art.

The term “calcium carbonate” has its traditionally meaning and included,for example and without limitation, ground calcium carbonate,precipitated calcium carbonate and needle calcium carbonate, each beingprepared in a variety of, for example and without limitation, purities,densities, fineness of grain, morphologies, surface areas, high oilabsorption, bulk densities from ultra-low to super high powderdensities, and the like.

The term “dilute sodium hydroxide” means sodium hydroxide, typically butnot limited to solid form, diluted with water to a concentration of notgreater than about 20 percent.

The term “first solution” means a solution of ammonium sulfate andsulfuric acid as further described herein and used in preparing asolubility enhancing aqueous composition.

The term “fill material” means at least one of calcium carbonate, Chinaclay, talc, titanium dioxide and/or one or more other material that istypically added to a substrate for the formation of a final paperproduct which includes in part, calcium carbonate. The term “fillmaterial”, when used more generally in reference to the enhancedcarbonate compositions of the present invention, has the traditionalmeaning as used in the art for the respective product in which theenhanced carbonate composition is used.

The term “free of solids” means that the solubility enhancing aqueouscomposition do not form salt crystals or other solids that remain in thecomposition over time, such salt crystals or other solids being formedfrom the reactants of ammonium sulfate and sulfuric acid.

The term “inhibition” or “inhibiting” means the act of prophylaxis,retarding and/or controlling the growth of microbes in products asdescribed herein.

The term “microbes” means, individually or collectively, bacteria,fungi, viruses and/or mold.

The term “paper” means paper and paperboard (single or multi-ply),unless otherwise differentiated, as each term is known in the art.

The term “paper and paperboard products(s) means, without limitation,any product that contains or is made from paper and/or paperboard inpart or in whole. One example of such products includes, withoutlimitation, cardboard.

The term “pulp” or “paper pulp” (used interchangeably) means any rawmaterial or combination of raw materials used for paper manufacture.Paper pulp or pulp can contain, for example and without limitation,vegetable, cellulosic, mineral and/or man-made fibers.

The term “reaction unit” relative to the preparation of a solubilityenhancing aqueous composition means the desired total volume of a firstsolution as expressed as a ratio of a range of ammonium sulfateconcentrations to sulfuric acid concentrations (the reactants).

The term “second solution” means the first solution as prepared for afinal volume plus the requisite amount of water to form a composition ofthe present invention as further described herein and used in preparinga solubility enhancing aqueous composition.

The term “sodium hydroxide solution” means a sodium hydroxide, typicallyin a dilute sodium hydroxide solution, wherein the solution can be anydilution as further set forth herein.

The term “solubility enhancing aqueous composition” means the solubilityenhancing aqueous compositions as described herein.

The term “sulfate anions” encompasses each of sulfate anions, bisulfateanions and combinations thereof. Combinations of sulfate anions andbisulfate anions are common in the solubility enhancing aqueouscompositions described herein.

The term “sulfuric acid” means concentrated sulfuric acid having aconcentration of from about 95% to about 98%.

The term “substantially free of solids” means that the solubilityenhancing aqueous compositions and/or the enhanced carbonatecompositions described herein are at least 95 percent aqueous or,alternatively, at least 98 percent aqueous without the formation of saltcrystals or other solids. The addition of materials not an element ofthe solubility enhancing aqueous compositions and/or carbonate enhancingcompositions in the preparation of compositions of the present inventionmay affect the amount of salts and/or other solids. As such, the term“substantially free of solids” pertains only to the preparations of eachof the solubility enhancing aqueous compositions and/or the carbonateenhancing compositions of the present invention described herein.

DESCRIPTION

The following description and examples are included to demonstrate theembodiments of the present disclosure. It should be appreciated by thoseof skill in the art that the compositions, techniques and methodsdisclosed in the examples herein function in the practice of thedisclosed embodiments. However, those skilled in the respective artsshould, in light of the present disclosure, appreciate that changes canbe made to the specific embodiments and still obtain a like or similarresult without departing from the spirit and scope of the disclosedembodiments.

The present specification includes references to “one aspect/embodiment”or “an aspect/embodiment”. These phrases do not necessarily refer to thesame embodiment although embodiments that include any combination of thefeatures or elements disclosed herein are generally contemplated unlessexpressly disclaimed herein. Particular features, processes, elements orcharacteristics may be combined in any suitable manner consistent withthis disclosure.

With the pulp-paper industry, at least two well-known problems existwith the use of calcium carbonate filler (e.g., precipitated, ground,needles and, without limitation, the like) incorporated into the paperweb during paper formation on the papermaking wire, particularlyincreased use of such filler: i. filler particles added to fibersuspended in water are not easily retained in the forming sheet becausethey are often too small to be entrapped mechanically and because fillerparticles are negatively charged, they repel each other; and ii. fillerparticles can interfere with fiber-fiber bonding; therefore, causingtensile strength of the paper to suffer. Also, the addition of calciumcarbonate beyond a certain level will cause, among other problems,reduced paper strength and stiffness, increased size demand, andincreased abrasion and dusting.

Moreover, there are four primary means by which filler, particularlycalcium carbonate, interacts with pulp fiber: i. calcium carbonate isdistributed among the fibers; ii. one end of calcium carbonate isembedded in one fiber with the other end embedded in another fiber; iii.one end of calcium carbonate is embedded in one fiber with the other endbeing distributed among the fibers; and iv. calcium carbonate isentirely embedded in a fiber. The challenge is to provide for anenvironment for fiber-filler entanglement and friction while alsoproviding for enhanced hydrogen bonding. The potential benefits can bean increase in filler loading, reducing fiber input and reducing papercosts, while maintaining the positive attributes typical of calciumcarbonate used as a filler in paper, which are many and well known inthe art.

Although filler particles (type and size) are frequently designed toaccommodate individual paper customer needs, there exists a wide rangeof filler introduced during this aspect of the paper making process. Forthe sake of clarity, as used herein, the term “paper” also includes“paper board” products in addition to products made from such paper andpaper board products. For example, and without limitation, calciumcarbonate fill is generally about 10% to about 30%, typically about 20%for printing paper. The introduction of calcium carbonate can be addedduring the process at the wet-end or as a surface application. Fillerlevel of up to about 50%, although not common, can be used for coatedpapers (e.g., wood-free 135 g/m2) and copy and office paper (75-80 g/m2with up to 30% filler used; although 15% filler is reported to be usedin North America for weight levels up to 75 g/m2). In essence, there area plethora of variables known in the paper preparation art which areincorporated into a variety of processes, including numerous forms offiller, particularly calcium carbonate, used to form a broad range ofpaper, including paper board, products. It is not the intent of thisdisclosure to reteach paper making processes. Rather, it is the intentto recite a representative sample of some of the processes, and relatedvariables, used in an intricate yet well-known art. As such, the use ofcalcium carbonate and, more specifically, carbonate enhancedcompositions of the present disclosure, is not to be limited to thebrief review of paper making processes disclosed herein. In fact, thecarbonate enhanced compositions of the present invention can be used inlieu of straight calcium carbonate regardless of form, as used inwet-end processing.

Without being held to a particular theory, it is believed that theaddition of at least one carbonate enhanced composition of the presentinvention compared to using straight calcium carbonate as a filler inpulp-based or other paper making processes modifies the zeta potentialof the calcium carbonate, potentially providing strongerbonds/interaction between the fiber and calcium carbonate filler. Theend result is a potentially higher percentage of calcium carbonate inthe wet-end without the negative attributes associated with increasedamounts of filler for each particular paper type. Such use of carbonateenhanced compositions of the present invention provides, withoutlimitation, excellent runnability, overall potential cost savings,improved hydrophobic sizing, opacity, and print characteristics, andimproved, or at least not a loss, of tensile, bond and/or burststrength, while potentially not affecting paper caliper or caliper posecompared to the use of non-enhanced calcium carbonate.

Accordingly, one aspect of the present invention provides a paperforming mixture comprising a paper making fiber and at least onecarbonate enhanced composition of the present invention.

Addition of such carbonate enhanced mixture is typically, withoutlimitation, added to the paper making process at the wet-end.

Further provided is a paper forming mixture comprising a pulp-basedmixture of pulp and at least one carbonate enhanced composition of thepresent invention.

Also provided is a paper forming mixture comprising a paper making fiberand at least one paper enhancing composition of the present invention.Addition of such paper enhancing composition is added, among other usesas set forth herein, to the paper making process at the wet-end.

Further provided is a paper forming mixture comprising a pulp-basedmixture of pulp and at least one paper enhancing composition of thepresent invention.

An additional aspect of the present invention provides a paper formingmixture comprising a pulp-based mixture of pulp and at least onecarbonate enhanced composition of the present invention, wherein theamount of calcium carbonate filler is at least five percent (5%) greaterthan the amount calcium carbonate fill typically added to a given papertype. For example, and without limitation, as reviewed in part above,for a paper type typically using 10-30% fill, the amount of fill thatcan be added to the paper forming wet mixture will equal at least 31.5%of the total wet mixture. This increase in calcium carbonate fill amountcan be used for any paper type well known to the skilled artisan.

An further aspect of the present invention provides for a method ofmodifying the zeta potential of calcium carbonate used in a paper makingprocess comprising the addition of at least one carbonate enhancedcomposition of the present invention to the wet-end of a paper makingprocess. More particularly, the present invention also provides a methodof modifying the zeta potential of calcium carbonate used in apulp-based paper making process comprising the addition of at least onecarbonate enhanced composition of the present invention to the wet-endof a paper making process.

The present invention further provides a method of increasing at leastone of the group consisting of paper tensile, bond and burst strength ofpaper comprising the addition of at least one carbonate enhancedcomposition of the present invention to the wet-end of a paper makingprocess compared to an equal amount of unenhanced calcium carbonate. Asused herein, the term “unenhanced calcium carbonate” means straightcalcium carbonate without the addition of at least one aqueous paperenhancing composition of the present invention.

A further aspect of the present invention provides a method ofincreasing at least one of the group consisting of paper tensile, bondand burst strength of paper comprising the addition of at least onecarbonate enhanced composition of the present invention to the wet-endof a paper making process compared to an equal amount of unenhancedcalcium carbonate without a decrease in at least one selected from thegroup consisting of runability, hydrophobic sizing, opacity and printcharacteristics.

An additional aspect of the present invention provides a method ofincreasing at least one of the group consisting of paper tensilestrength, bond strength and burst strength of paper comprising theaddition of at least one carbonate enhanced composition of the presentinvention to the wet-end of a paper making process compared to an equalamount of unenhanced calcium carbonate without an increase in caliperpose.

Further provided is a method of increasing the amount of calciumcarbonate filler particles retained in a paper forming sheet to fibersuspended in water during the paper making process comprising theaddition of at least one carbonate enhanced composition of the presentinvention to the wet-end of a paper making process compared to an equalamount of unenhanced calcium carbonate.

As taught herein, the addition of a carbonate enhanced composition ofthe present invention, through the modification of carbonate zetapotential and otherwise, has the potential to form more and tighterbonds among the fiber and fill than is otherwise typically the case whenusing only unenhanced calcium carbonate as a fill rather than at leastone carbonate enhanced composition of the present invention. As such,the pores of the paper can be reduced with the use of the carbonateenhanced composition resulting in paper that is less penetrable to dustand other particulate matter, pollutants and microorganisms.Accordingly, another aspect of the present invention provides for amethod of decreasing the pore size of paper comprising the addition ofat least one carbonate enhanced composition of the present invention tothe wet-end of a paper making process compared to an equal amount ofunenhanced calcium carbonate. This phenomenon also provides for a methodof preparing paper for medical and industrial protective uses comprisingthe addition of at least one carbonate enhanced composition of thepresent invention to the wet-end of a paper making process.

As further referenced herein, the carbonate enhanced compositions of thepresent invention also provide antimicrobial activity. Accordingly, anadditional aspect of the present invention provides for antimicrobialpaper, having a multitude of uses, comprising paper prepared by theaddition of at least one carbonate enhanced composition of the presentinvention to the wet-end of a paper making process; such paper beinguseful for the inhibition of microbes.

A further aspect of the present invention provides a carbonate enhancedcomposition comprising silver carbonate and at least one aqueouscarbonate enhancing composition. Also provided is a method of using atleast one such carbonate enhanced composition in the preparations of atleast one product using silver carbonate in its composition.

Further provided is a carbonate enhancing composition and a carbonateenhanced composition wherein at least silver sulfate is added to eachsuch composition, either as the sole sulfate or in combination withcopper sulfate. In essence, silver sulfate can be substituted for coppersulfate or used in combination with copper sulfate wherein theconcentration of copper sulfate and/or silver sulfate in the presentcompositions as if copper sulfate alone is used. The same applies forthe use of copper sulfate and/or silver sulfate in the paper enhancingcompositions of the present invention.

An additional aspect of the present invention provides a carbonateenhanced composition comprising at least one organic compound carbonateand at least one aqueous carbonate enhancing composition. Also providedis a method of using a composition comprising at least one organiccompound carbonate and at least one carbonate enhanced composition inthe preparations of at least one product using at least one organiccompound carbonate in its composition.

To prepare the carbonate enhanced compositions for use in the papermaking process when calcium carbonate is used as at least one filler, atleast 1.5 pounds of at least one carbonate enhancing composition of thepresent disclosure is added, typically as a spray designed to providethorough coverage of the calcium carbonate particles, to each ton of oneor more selected calcium carbonate products. Up to ten pounds or greaterof carbonate enhancing composition per ton of calcium carbonate can beused to prepare a carbonate enhanced compositions for use in paper. Moreparticularly, any whole or fractional number of the enumerated range ofpounds of carbonate enhancing composition per ton of calcium carbonateis used to prepare a carbonate enhanced composition for use in paper.The use of the term “ton” as used herein refers to the U.S. ton. Slightadjustments of the amount of addition of a carbonate enhancingcomposition per ton of calcium carbonate may have to be made if tonnageis determined as metric tons or a British (long) ton. Any calciumcarbonate product(s) used as filler for making paper can be used toprepare carbonate enhanced compositions of the present invention.Selection of the amount of carbonate enhancing composition added tocalcium carbonate to prepare carbonate enhanced compositions for use inpaper may be judicially selected by the manufacturer of either thecalcium carbonate and/or the paper producer based on the type of paper(including paper board) and/or the use of the paper product(s).Furthermore, the use of carbonate enhanced compositions of the presentinvention should not be restricted by the use of other additivestypically used in the paper manufacturing process.

To impart the antimicrobial properties in paper referenced herein,typically, at least 5 pounds of carbonate enhancing composition is usedfor each ton of calcium carbonate to form carbonate enhancedcompositions although less may be adequate for certain paper uses. Moreparticularly, the amount of calcium enhancing composition added tocalcium carbonate for such antimicrobial uses in paper is, for example,5 pounds, 6 pounds, 7 pounds, 8 pounds, 9 pounds, 10 pounds, 11 poundsand greater than 12 pounds, or any fractional number thereof, per ton ofcalcium carbonate.

For paper pulp, at least one carbonate enhanced composition, typicallyusing calcium carbonate, can also be used as a causticizing agent in thepulp sulfate process, to prepare calcium bisulfate in the pulp sulfiteprocess, used with chlorine in the bleaching process, in the treatmentof pulp and paper mill waste treatment, a filtration conditioner, aneutralizing agent and to recover alcohol, calcium lignosulfonate andyeast.

The present invention further provides a paper enhancing compositioncomprising water, at least one solubility enhancing aqueous composition,sodium hydroxide, copper sulfate and, optionally, at least onesurfactant selected from the group consisting of non-ionic surfactantsand/or anionic surfactants.

An additional aspect of the present invention provides an aqueous or,substantially aqueous, paper enhancing composition (aqueousnotwithstanding the potential for copper sulfate to not have completelydissolved in the paper enhancing composition) comprising an aqueousphase comprising a solubility enhancing aqueous composition wherein 1part of a first solution is added to about 15 to about 20 parts ofwater, frequently deionized water, to form a second solution; sodiumhydroxide solution having a concentration of about 5% to about 7.5%volume/volume of the total aqueous phase volume of the composition; atleast one surfactant selected from the group consisting of non-ionicsurfactants and anionic surfactants having a concentration from about0.05 percent to about 0.15 percent volume/volume of the total aqueousphase volume of the composition; and copper sulfate having aconcentration from about 20 percent to about 26 percent mass/volume ofthe total aqueous phase volume of the composition. The use of suchsurfactant in the present composition is optional. As used herein, theterm “aqueous paper enhancing composition” also includes any suchcomposition that is substantially aqueous as indicated above.

A further aspect of the present invention further comprises the additionof an acid or base to adjust the pH to a pH from about 2.5 to about 3.5to the immediately preceding composition. There are multiple potentialuses of such paper enhancing compositions throughout paper making andpaper finishing processes. For example, paper enhancing compositions ofthe present invention can be added directly to the wet-end process ofpaper production for use as, for example, a paper coagulator and/or toprovide microbial control.

As a coagulator, the addition of at least one paper enhancingcomposition to the wet-end of paper production can increase the tensilestrength, bond strength and/or burst strength of paper through multipleactions. Without being held to a particular theory, it is believed thatthe addition of at least one paper enhancing composition of the presentinvention creates an environment wherein the fiber(s) used in papermaking, with or without the presence of calcium carbonate as a fillmaterial, enhances the attraction of the fibers, narrowing theinterstitial spaces between and among fibers creating smaller poreswhile increasing the tensile, bond and/or burst strength of theresulting paper. The purpose for using such paper enhancing compositionsin this context is to impart additional paper strength compared to paperproduced without the use of such paper enhancing compositions withoutaffecting paper caliper or pose or, alternatively, increased amount ofsuch paper enhancing compositions can be used to increase the density ofthe resulting paper for a variety of uses including, for example andwithout limitation, preparation of paper, frequently in the form ofmasks, used for industrial and/or medical use wherein the passage ofpollutions and/or microorganisms are retarded or prevented.

Accordingly, the present invention further provides a method ofincreasing at least one of paper tensile strength, bond strength andburst strength compared to paper prepared without the addition of atleast one paper enhancing composition comprising the addition of atleast one paper enhancing composition to the wet-end of the paper makingprocess.

Another aspect of the present invention provides a method for decreasingthe interstitial pore size between and among paper fibers in a wet-endpaper making process compared to paper prepared without the addition ofat least one paper enhancing composition comprising the addition of atleast one paper enhancing composition to the wet-end of the paper makingprocess.

An additional aspect of the present invention provides a method forincreasing paper density compared to paper prepared without the additionof at least one paper enhancing composition comprising the addition ofat least one paper enhancing composition to the wet-end of the papermaking process.

A further aspect of the present invention provides for paper havingantimicrobial properties comprising paper prepared using at least onepaper enhancing composition during the wet-end process stage of papermaking; such paper being useful for the inhibition of microbes.

It is believed that the addition of at least one paper enhancingcomposition of the present invention modifies the zeta potential of thecalcium carbonate, when calcium carbonate is used as a filler material,modifying the charge of the calcium carbonate and potentially providingstronger bond/interaction between the fiber and calcium carbonatefiller. Such modification of the zeta potential frequently provides anincrease in the zeta potential although a decrease of zeta potential ispossible depending upon the mixture to which at least one paperenhancing composition is added.

Accordingly, also provided herein is a method of modifying the zetapotential of calcium carbonate when used in the paper making processcomprising applying at least one aqueous paper enhancing compositionduring the wet-end stage of paper production.

More particularly, the present invention also provides a method ofmodifying the zeta potential of calcium carbonate when used in apulp-based paper making process comprising applying at least one aqueouspaper enhancing composition during the wet-end stage of paperproduction.

To use the aqueous paper enhancing compositions and impart the benefitsof the use thereof including, for example and without limitation, papercoagulation and antimicrobial activity, at least one aqueous paperenhancing compositions is added to the wet-end of a paper making processat a concentration of about at least 1,500 ppm of the total weight ofthe wet-end mixture to which the paper enhancing composition(s) is/areadded. More specific amounts of paper enhancing compositions (aqueous orsubstantially aqueous) are added to the wet-end processes atconcentrations of about 1,500 ppm, about 2,500 ppm, about 3,500 ppm,about 4,500 ppm, about 5,500 ppm, about 6,500 ppm or greater than about7,000 ppm of the wet-end mixture to which the paper enhancingcomposition(s) is/are added. Moreover, any whole or fractional number ofppm of the stated range of paper enhancing composition may be added tothe wet-end mixture to which the paper enhancing composition(s) is/areadded. Selection of the amount of paper enhancing composition added tothe wet-end mixture to which the paper enhancing composition(s) is/areadded may be judicially selected by the paper producer based on the typeof paper (including paper board) and/or the intended use of the paperproduct(s). Furthermore, the use of paper enhanced compositions of thepresent invention should not be restricted by the use of other additivestypically used in the paper manufacturing process.

To impart the antimicrobial properties in paper referenced herein,typically, at least 2,500 ppm of the at least one paper enhancingcomposition is added or applied per ton of the wet-end mixture to whichthe paper enhancing composition(s) is/are added. More particularly, theamount of paper enhancing composition added or applied to the wet-endmixture to which the paper enhancing composition(s) is/are added forsuch antimicrobial uses in paper is, for example, about 2,500 ppm, about3,500 ppm, about 4,500 ppm and greater than about 5,000 ppm, or anywhole or fractional number thereof, per ton of wet-end mixture.

Notwithstanding the teachings for wet-end use of carbonate enhancingcompositions and paper enhancing compositions of the present invention,a paper producer may not wish to enhance all of the paper produced frompulp or another fiber to the final product. It is beneficial for a paperproducers to select which paper products may be treated to impartadditional qualities to the final paper products. Such additionalqualities can be imparted into or onto paper via the application of apaper enhancing composition of the present invention via application ofsuch composition onto paper before, during or after the wet press aspectof paper production. Typically, after the wet-end step of paperproduction is completed, the mix of fiber, filler and any additionalcomponents is fed through a series of high pressure rollers for thepurpose of squeezing out a substantial amount of water from the wet-endprior to the paper entering dryer and calendar sections. High pressureroller systems can be fitted with spray nozzles before, during or afterthe wet press section. It is throughout this wet press section of paperprocessing that one or more paper enhancing compositions of the presentinvention is/are sprayed onto the paper.

Application, typically as a spray, of at least one paper enhancingcomposition onto paper entering, during or following the wet presssection of the paper making process can impart the same and additionalbenefits and attributes to paper as with the use of adding at least onecarbonate enhanced composition and/or at least one paper enhancingcomposition of the present invention during the wet-end process asdescribed herein. As such, application of at least one aqueous paperenhancing composition of the present invention can provide increasedtensile, bond strength and/or burst strength to the respective paper,modify the zeta potential of calcium carbonate or at least one enhancedcarbonate composition of the present invention used in the paper makingprocess applied when the paper carries a substantial amount ofwater/moisture (e.g., the earlier to mid stages of the wet pressprocess), improved hydrophobic sizing, opacity, and printcharacteristics, while potentially not affecting paper caliper orcaliper pose unless otherwise intended. When desired, however, thedensity of paper can be increased by reducing pore spaces between andamong the fiber and/or fill particles via the application of at leastone aqueous paper enhancing composition of the present invention duringthe wet press stage of production. The resulting paper can be used formedical and industrial applications providing improved safety comparedto products prepared without the benefit of the aqueous paper enhancingcompositions. As further referenced herein, the aqueous paper enhancingcompositions of the present invention also provide antimicrobialactivity into and potentially throughout the paper onto which thepresent composition is applied during the wet press process of papermaking. Collectively, the attributes presented in this paragraphrepresents, for the purposed herein, as “enhanced paper”, and theprocess of preparing enhanced paper as “enhancing paper”.

Accordingly, another aspect of the present invention provides forenhanced paper comprising paper having applied during the wet pressstage of paper production at least one aqueous enhancing papercomposition.

Further provided herein are the following methods:

-   -   A method of enhancing paper comprising applying at least one        aqueous paper enhancing composition during the wet press stage        of paper production.    -   A method of increasing at least one of the group consisting of        tensile strength, bond strength and burst strength in paper        compared to the respective tensile strength, bond strength and        burst strength of paper untreated with an aqueous paper        enhancing composition comprising applying at least one aqueous        paper enhancing composition during the wet press stage of paper        production.    -   A method of modifying the zeta potential of calcium carbonate        when used in the paper making process comprising applying at        least one aqueous paper enhancing composition during the wet        press stage of paper production.    -   The present invention also provides a method of modifying the        zeta potential of calcium carbonate used in a pulp-based paper        making process comprising applying at least one aqueous paper        enhancing composition during the wet press stage of paper        production.    -   A method of increasing at least one of the group consisting of        paper tensile strength, bond strength and burst strength of        paper comprising applying at least one aqueous paper enhancing        composition during the wet press stage of paper production        compared to paper untreated with an aqueous paper enhancing        composition without an increase in caliper pose.    -   A method of decreasing the pore size of paper comprising        applying at least one aqueous paper enhancing composition during        the wet press stage of paper production compared to paper        untreated with an aqueous paper enhancing composition. This        method typically requires the use of such compositions at        concentrations in the higher end of the stated ranges.    -   A method of preparing paper for medical and industrial        protective uses comprising applying at least one aqueous paper        enhancing composition during the wet press stage of paper        production.    -   A method of preparing paper for use in masks for mammalian,        particularly human, use comprising applying at least one aqueous        paper enhancing composition during the wet press stage of paper        production.

Further provided is antimicrobial paper, having a multitude of uses,comprising paper prepared by the application of at least one aqueouspaper enhancing composition of the present invention during the wetpress stage of paper production.

To use the aqueous paper enhancing compositions and impart the benefitsof the use thereof including, for example and without limitation, paperstrengthening and antimicrobial activity, at least one aqueous paperenhancing compositions is applied, typically as a spray, before, duringor after the wet press stage of a paper making at a concentration ofabout at least 1,500 ppm of such composition to each ton of wet weightmatter entering the wet press stage. More specifically, amounts of paperenhancing compositions are applied as a spray during the wet press stageof paper making at concentrations of about 1,500 ppm, about 2,500 ppm,about 3,500 ppm, about 4,500 ppm, about 5,500 ppm, about 6,500 ppm orgreater than about 7,000 ppm to each ton of wet weight matter enteringthe wet press stage of paper making. Generally, concentrations of paperenhancing compositions can be reduced at later stages of the wet pressstage if the spray containing paper enhancing compositions is appliedafter a substantial amount of moisture is removed. However, if the spraycontaining paper enhancing compositions of the present invention isapplied once the paper is substantially dry but prior to entering thedrying process, it is suggested to use the spray concentrations setforth below for paper coatings. However, slightly higher concentrationsshould be used based on the amount of residual moisture prior to suchdrying stage. Moreover, any whole or fractional number of ppm, withinthe stated concentration range, of paper enhancing composition may beapplied during the wet press stage. Selection of the amount of paperenhancing composition applied during the wet press stage may bejudicially selected by the paper producer based on the type of paper(including paper board) and/or the use of the paper product(s).Furthermore, the use of paper enhanced compositions of the presentinvention should not be restricted by the use of other additivestypically used in the paper manufacturing process.

To impart the antimicrobial properties in paper referenced herein,typically, at least 2,500 ppm of the at least one paper enhancingcomposition is applied for each ton of wet weight matter entering thewet press stage. More particularly, the amount of paper enhancingcomposition applied during the wet press stage for such antimicrobialuses in paper is, for example, about 2,500 ppm, about 3,500 ppm, about4,500 ppm and greater than about 5,000 ppm, or any whole or fractionalnumber thereof, per ton of wet weight matter entering the wet pressstage of paper production. The amount of paper enhancing compositionused can be adjusted pursuant to the recommendations set forth in theimmediately preceding paragraph.

Alternatively, at least one of the aqueous paper enhancing compositionsof the present invention can be applied to paper as an additive tosurface sizing, wherever surface sizing is applied throughout the paperand or paper printing processes. The concentrations of at least onepaper enhancing composition of the present invention when applied withsizing are the same concentrations taught herein below for theconcentrations used for paper coatings. The only difference is that theconcentrations are based on the total volume of sizing being surfaceapplied to paper rather than the total volume of paper coating(s) beingapplied. As such, a minimum recommended concentration of at least onepaper enhancing composition of the present invention to be applied withsurface sizing is at least about 1,500 ppm of the total sizing volumebeing surface applied for general use and benefit; and at least about2,500 ppm of such paper enhancing composition when antimicrobialactivity is desired.

For each use of an aqueous paper enhancing compositions of the presentinvention, application during the paper making process as describedabove or when used as paper coatings as described below, suchcompositions can be applied individually or in combination with otheradditives and/or coating material as such materials are used in thepaper making/processing arts.

Applications of at least one aqueous paper enhancing composition of thepresent invention can also be applied directly to finished paper at anytime following the dryer section of the paper making process. In otherwords, such application can be made from the calender section of papermaking through and following printing thorough a printing press or otherprinting method; or, alternatively, to prepare paper products ordirectly to final paper products.

In addition to coatings being applied by the paper manufacturer, liquidcoatings are frequently applied in-line by the printer as part of theprinting process or off-line after the project leaves the press.Although the paper enhancing compositions of the present invention canbe applied with any liquid coating, the present paper enhancingcompositions are typically applied with commonly used or specialtyaqueous coatings that are usually flooded across the entire sheet.Different coatings are available in different finishes, tints, texturesand thicknesses, which may be used to adjust the level of protection orachieve different visual effects. Areas that are heavily covered withblack ink or other dark colors often receive a protective coating toguard against fingerprints, which stand out against a dark background.Coatings are also used on magazine and report covers and on otherpublications that are subject to rough or frequent handling. Moreover,communicable diseases caused by microorganisms, particularly, withoutlimitation bacteria, including MRSA, and viruses such as noroviruses andcoronaviruses, each of which, along with other pathogens, have theability to remain viable and transmissible on surfaces, including paper,for a period of time. Accordingly, it is beneficial to have additionalmaterials that can be added to liquid paper coatings to impartattributes such as additional tensile strength, bond strength and/orburst strength to coated paper. Additionally, it is beneficial toprovide antimicrobial attributes to the surface of paper throughcoatings. Each of these attributes can be added to paper via theapplication of at least one paper enhancing composition of the presentinvention as a component in other liquid, commonly aqueous, papercoatings or at a particular concentration to other acceptable papercoating media, including water. Coatings including at least one paperenhancing composition of the present invention can be applied via anymethod used in the paper coating industry including, for example andwithout limitation, flood coating, blade coating, premetered filmpresses and roll metering. Each type of coating has particular uses,benefits and drawbacks. As such, the applier of such coatings can selectthe best coating and type of application for each such coatingapplication. Accordingly, the application of at least one paperenhancing composition of the present invention should not be limited bythe type of paper coating or method of application.

As such, another aspect of the present invention provides for a papercoating comprising at least one aqueous paper enhancing composition.

An additional aspect provides for paper coated with at least one aqueouspaper enhancing composition.

Another aspect of the present invention provides a method of increasingat least one of the group consisting of paper tensile strength, bondstrength and burst strength of paper comprising the application of acoating to paper comprising at least one paper enhancing composition ofthe present invention.

Paper, including the printing on paper, can also be enhanced andprotected by a variety of well-known liquid additives. The presentaqueous paper enhancing compositions of the present invention, whenapplied as paper coatings alone or in combination with other papercoating materials including, for example and without limitation, varnishand ultra violet coatings, can also provide, for example and withoutlimitation: protection from fingerprints and other blemishes, helpprevent metallic inks from tarnishing, and provide surfaces that can bewritten on with pencil, pen, ink jet printers, laser jet printers,off-set printers and the like. Although the present aqueous paperenhancing compositions can be applied to paper, in general, it may bebest to use 80# text weight or heavier paper stocks to keep the paperfrom becoming curled or wrinkled, particularly when using a floodcoating method.

An additional aspect of the present invention provides for a method ofproviding at least one of protection from fingerprints and otherblemishes, help prevent metallic inks from tarnishing, and provide papersurfaces that can be written on with multiple media (including, withoutlimitation, pencil, pen, ink jet printers, laser jet printers, off-setprinters and the like) comprising the application of a coating to papercomprising at least one paper enhancing composition of the presentinvention.

A further aspect of the present invention provides for a method ofproviding improvement of at least one of protection from fingerprintsand other blemishes, help prevent metallic inks from tarnishing, andprovide paper surfaces that can be written on with multiple media(including, without limitation, pencil, pen, ink jet printers, laser jetprinters, off-set printers and the like) compared to paper coatings notincluding the application of at least one aqueous paper enhancingcomposition of the present invention comprising the application of acoating to paper comprising at least one paper enhancing composition ofthe present invention.

Because of the antimicrobial activity of the present paper enhancingcompositions of the present invention, such compositions can be used ascoatings to paper to provide such antimicrobial activity. Paper coatedwith such compositions have almost unlimited uses including, for exampleand without limitation, construction of masks used for industrialpollutants and/or medical masks used by any individuals includingmedical and first-responder personnel, paper used for wrapping foodproducts including produce and/or fish and/or meat products, paper usedas or in diapers, papers used as diapers, in produce and/or fish and/ormeat products (for example, the absorbent paper underlining packagedpoultry products), packaging, generally, blotters used by childrenand/or adults, facial tissues, sanitary napkins, liners for fruit, orany of a plethora of other paper uses where the inhibition ofmicroorganism is desired and/or required.

Accordingly, another aspect of the present invention provides for coatedpaper having antimicrobial activity comprising paper coated with atleast one aqueous paper enhancing composition of the present invention.

An additional aspect of the present invention provides for paper havingantimicrobial properties comprising paper coated with at least oneaqueous paper enhancing composition of the present invention.

Another aspect of the present invention provides for a method ofpreparing paper having antimicrobial activity comprising applying as acoating to paper at least one aqueous paper enhancing composition of thepresent invention to said paper.

Further provided is antimicrobial paper, having a multitude of uses,comprising paper prepared by the application of a coating of at leastone aqueous paper enhancing composition of the present invention duringthe wet press stage of paper production.

Because of the antimicrobial activity of paper coated with at least onesuch aqueous paper enhancing composition, such coated paper can protectand potentially prolong the shelf-life of produce, meats and otherperishable foodstuff (collectively, “foodstuff”). As such, anotheraspect of the present invention provides a method of extending theshelf-life of perishable foodstuff comprising placing such foodstuff incontact, in whole or in part, with paper coated with at least oneaqueous paper enhancing composition of the present invention. Suchshelf-life can be extended for at least 24 hours, providing substantialvalue to providers of such perishable foodstuff.

Another aspect provides a method for preparing paper for medical andindustrial protective uses comprising applying as a coating to paper atleast one aqueous paper enhancing composition during.

An additional aspect provides a method of preparing paper for use inmasks for mammalian, particularly human, use comprising applying as acoating at least one aqueous paper enhancing composition.

Aqueous paper enhancing compositions of the present invention areapplied to paper as coatings, either as a single coating in aliquid-based solution, frequently water, or as at least one componentwith other surface-applied paper coating materials at a concentration ofat least about 1,500 ppm of the total amount of liquid-based solution orcoating being applied. More specifically, amounts of paper enhancingcompositions are applied as a spray coating at concentrations of about1,500 ppm, about 2,500 ppm, about 3,500 ppm, about 4,500 ppm, about5,500 ppm, about 6,500 ppm or greater than about 7,000 ppm of the totalamount of liquid-based solution or coating being applied. Moreover, anywhole or fractional number of ppm of paper enhancing composition, withinthe given concentration range, may be applied during the coatingprocess. Selection of the amount of paper enhancing composition appliedduring the coating process stage may be judicially selected by the paperproducer, printer, or desire of the end user based on the type of paper(including paper board) and/or the use of the paper product(s).

To impart the antimicrobial properties in paper referenced herein,typically, aqueous paper enhancing compositions of the present inventionare applied to paper as coatings, either as a single coating in aliquid-based solution, frequently water, or as at least one componentwith other surface-applied paper coating materials at a concentration ofat least about 2,500 ppm of the total amount of liquid-based solution orcoating being applied. More specifically, to provide antimicrobialproperties to paper coatings, amounts of paper enhancing compositionsare applied as a spray coating at concentrations of about 2,500 ppm,about 3,500 ppm, about 4,500 ppm, about 5,500 ppm, about 6,500 ppm orgreater than about 7,000 ppm of the total amount of liquid-basedsolution or coating being applied to the paper. Moreover, any whole orfractional number of ppm of paper enhancing composition within the givenconcentration range, may be applied during the coating process.Selection of the amount of paper enhancing composition applied duringthe coating process stage may be judicially selected by the paperproducer, printer, or desire of the end user based on the type of paper(including paper board) and/or the use of the paper product(s).

For each of the claims set forth herein below, such claims can bealternatively drafted using “consisting of” and “consisting essentiallyof” claim language.

One element of the present paper enhancing compositions and carbonateenhancing compositions of the present invention provides a solubilityenhancing aqueous composition comprising a first solution comprising ananionic component consisting essentially of sulfate ions, alone or incombination with bisulfate ions, having a concentration from about 8.00moles per liter to about 13.00 moles per liter of the first solutionvolume, and a cationic component consisting essentially of ammonium ionshaving a concentration from about 1.45 moles per liter to about 2.01moles per liter of the first solution volume, combined with a volume ofwater at least equal to the volume of the first solution forming asecond solution. Generally, the first solution of this composition willalso comprise hydrogen ions in a concentration from about 17.38 to about21.68 moles per liter of the total volume of the first solution.

An alternative element of the present paper enhancing compositionprovides a solubility enhancing aqueous composition comprising a firstsolution comprising an anionic component comprising sulfate ions, aloneor in combination with bisulfate ions, having a concentration from about8.00 moles per liter to about 13.00 moles per liter of the firstsolution volume, and a cationic comprising ammonium ions having aconcentration from about 1.45 moles per liter to about 2.01 moles perliter of the first solution volume, combined with a volume of water atleast equal to the volume of the first solution forming a secondsolution. Generally, the first solution of this composition will alsocomprise hydrogen ions in a concentration from about 17.38 to about21.68 moles per liter of the total volume of the first solution.

It is the intent of the present disclosure to permit the skilled artisanto prepare a solubility enhancing aqueous composition element using arange of water in a ratio to the concentrations of ammonium sulfate andsulfuric acid for each preparation, with the resultant sulfate anionsand ammonium cations, and the amount of water to be determined by suchartisan, each within the parameters taught herein.

For the sake of clarity, three solutions are formed in preparing thesecond solution which comprise solubility enhancing aqueouscompositions: 1) ammonium sulfate stock solution; 2) a first solutioncomprising the ammonium sulfate stock solution in sulfuric acid; and 3)second solution comprising solubility enhancing aqueous compositions.Unless context otherwise dictates, general references to the use of afirst solution and a second solution refers to the preparation of thereferenced solubility enhancing aqueous compositions used in thepreparation of paper enhancing agent compositions of the presentinvention.

To prepare the first solution of a composition of the presentdisclosure, one needs to first prepare an ammonium sulfate stocksolution. For example and without limitation, an ammonium sulfate stocksolution is prepared to contain 20%, 24%, 30%, 40%, 50% or 60% ofammonium sulfate in water, typically, without restriction, deionizedwater. For the sake of clarity, the percent concentration of ammoniumsulfate can be any whole number or fraction thereof in a range fromabout 20% to about 60%. The molar concentration of the stock solutionvaries by the ammonium sulfate concentration in a known volume of water.

By means of exemplification, the following calculations are used todetermine the amount of ammonium sulfate and sulfuric acid to add toform a first solution.

Ammonium Sulfate:

-   -   Ammonium sulfate equals 132.14 grams per mole. Using, for        example, a 24% ammonium sulfate solution, such solution would        have 240 grams of ammonium sulfate per 1 L of water. Because the        ratio of ammonium sulfate to sulfuric acid in this        exemplification is about 48% ammonium sulfate to about 52%        sulfuric acid, the first solution would contain 115.20 grams of        ammonium sulfate, equaling 0.872 moles per liter. As such, one        mole of ammonium sulfate provides 2 moles of ammonium and 1 mole        of sulfate. Accordingly, 0.872 moles of ammonium sulfate        provides to the ammonium sulfate stock solution 1.744 moles of        ammonium and 0.872 moles of sulfate required per liter of        reaction in forming the first solution.

Sulfuric Acid (Concentrated):

-   -   Sulfuric acid equals 98.079 g/mole as concentrated (95% to 98%)        reagent grade sulfuric acid. Sulfuric acid exists as a liquid        and has a density of 1.840 g/mL. For this example, sulfuric acid        comprises 52% of a first solution of 1 liter. As such, 520 mL        (0.52 L) of sulfuric acid is added to the ammonium sulfate stock        solution. 520 mL times 1.840 g/mL equals 956.8 grams. 956.8        grams divided by 98.079 grams per mole provides the target        concentration of 9.755 moles of sulfuric acid per liter of        preparation. 9.755 moles of sulfuric acid provides 9.755 moles        of sulfate anion and 2 moles of hydrogen resulting from each        mole of acid, in this example, 19.51 moles of hydrogen per liter        of said first solution.

Reaction Unit:

-   -   Using the values set forth above, in this instance, there are        about 0.872 moles of ammonium sulfate to about 9.755 moles of        sulfuric acid providing:        -   about 0.872 moles of ammonium sulfate provides about 0.872            moles of sulfate and about 1.744 moles of ammonium required            per reaction unit liter; and        -   about 9.755 moles per liter of sulfuric acid provides about            9.755 moles of sulfate anion and about 19.51 moles of            hydrogen per liter of reaction unit.    -   Using this example, each reaction unit, forming a first        solution, would contain:        -   about 0.972 moles of sulfate (from ammonium sulfate) plus            about 9.755 moles of sulfate from ammonium sulfate equaling            about 10.627 moles of sulfate anion per liter comprising            sulfate anions alone, bisulfate anions alone or, typically,            a mixture of sulfate and bisulfate anions;        -   about 1.744 moles of ammonium per liter; and        -   about 19.51 moles of hydrogen per liter.

To accomplish the formation of a solubility enhancing aqueouscomposition, a second solution is formed by the addition of water, acritical component, in an appropriate amount, to provide solubilityenhancing aqueous compositions that are substantially free, or free, ofsolids. Alternatively, a first solution can be added to the appropriateamount of water to form a second solution. As such, the order ofaddition of a first solution to water or water to the first solution toform a second solution is not of consequence. Use of the solubilityenhancing aqueous compositions may form solids when combined with otherchemical or other materials when using such solubility enhancing aqueouscompositions for its intended purpose: enhancing solubility of suchchemical compounds or other materials.

Generally, water is at least fifty percent of the second solution thatrepresents the solubility enhancing aqueous compositions. Moreover,water can comprise from at least fifty percent up to ninety-nine percentof the second solution or final composition. However, the lowerconcentrations of water, as taught herein, are typically more useful forfurther use of the present compositions used for solubility enhancement.Accordingly, the amount of water used to form a second solution is atleast 50% of the volume of the first solution or at least 50% of themass of the first solution. Alternatively, the mass of the sum of theammonium ion concentration plus sulfate ion concentration in a firstsolution can also serve as the basis of the amount of water to be addedto form a second solution wherein the amount of water added, by mass, toform a second solution equals at least 50% of the sum of the mass ofammonium ions plus sulfate ions. Another means by which to represent theamount of water added to the first solution is that the amount of waterused to form a second solution is at least equal to the volume of thefirst solution or at least equal to the mass of the first solution.Alternatively, the mass of the sum of the ammonium ions plus sulfateions in a first solution can also serve as the basis of the amount ofwater to be added to form a second solution wherein the amount of totalwater, including the water used to solubilize the ammonium sulfate andadded water, is at least equal to the sum of the mass of ammonium ionsplus sulfate ions.

The amount of water used to prepare the second solution, representingsolubility enhancing aqueous compositions, can be calculated involume/volume (total volume of the first solution plus at least the samevolume of water). Alternatively, the ratio of reactants to water(mass/mass) may be used. Using the values for ammonium sulfate andsulfuric acid from the above example, 115.20 grams of ammonium sulfateand 956.8 grams of sulfuric acid were used providing a sum of 1072 gramsof reactants. Accordingly, for water to equal at least fifty percent ofthe final composition, at least 1072 grams of water are added to thefirst solution to form the second solution, a solubility enhancingaqueous composition. Alternatively, as referenced above, the amount ofwater used to form a second solution can be based on the total mass orvolume of the first solution. Accordingly, any method taught herein canbe used for calculating the amount of water required to form a secondsolution. As taught above, using the mass of the reactants to dictatethe amount of water required to form a second solution is the minimumamount of water required to provide an aqueous solution and to impartthe qualities of the compositions of the present invention as furtherdelineated herein.

To achieve solubility enhancement, ranges of concentration of sulfateions and ammonium ions in the solubility enhancing aqueous compositionsare used while maintaining solubility enhancing aqueous compositionsthat are essentially free or are free of salt crystals or other solidsfrom the reactants that form a first solution. Accordingly, a firstsolution comprises an anionic component consisting essentially ofsulfate ions, alone or in combination with bisulfate ions, has aconcentration range from about 8.00 moles per liter to about 13.00 molesper liter of the first solution volume. The first solution alsocomprises a cationic component consisting essentially of ammonium ionshas a concentration from about 1.45 moles per liter to about 2.01 molesper liter of the first solution volume. Typically, when the lower valueswithin the range for sulfate ions are selected for preparing a firstsolution, a lower value within the stated range for ammonium ions isselected and included in the preparation of the first solution.Similarly, when higher values within the stated range for sulfate ionsare selected for the preparation of a first solution, higher values ofammonium ions are selected for the preparation of a first solution.Although not imperative, typically, the sulfate ion concentration withinthe given range of from about 8.00 moles per liter to about 13.00 molesper liter of first solution volume is proportionally commensurate withthe range of ammonium ion concentration within the given the given rangeof from about 1.45 moles per liter to about 2.01 moles per liter offirst solution volume.

In another embodiment of the solubility enhancing aqueous compositions,a first solution comprises an anionic component comprising sulfate ions,alone or in combination with bisulfate ions, has a concentration rangefrom about 8.00 moles per liter to about 13.00 moles per liter of thefirst solution volume. The first solution also comprises a cationiccomponent comprising ammonium ions has a concentration from about 1.45moles per liter to about 2.01 moles per liter of the first solutionvolume. Typically, when the lower values within the range for sulfateions are selected for preparing a first solution, a lower value withinthe stated range for ammonium ions is selected and included in thepreparation of the first solution. Similarly, when higher values withinthe stated range for sulfate ions are selected for the preparation of afirst solution, higher values of ammonium ions are selected for thepreparation of a first solution. Although not imperative, typically, thesulfate ion concentration within the given range of from about 8.00moles per liter to about 13.00 moles per liter of first solution volumeis proportionally commensurate with the range of ammonium ionconcentration within the given the given range of from about 1.45 molesper liter to about 2.01 moles per liter of first solution volume. Whenprepared according to the solubility enhancing aqueous compositionembodiments provided herein, the resulting hydrogen ion concentrationwill typically fall within the range from about 17.38 moles per liter toabout 21.68 moles per liter of first solution volume but falling withinthis hydrogen range is not necessarily critical to the final firstsolution but is beneficial when using the solubility enhancing aqueouscompositions for enhancing solubility of compounds or other materialsdepending upon the nature thereof.

The process for preparing the solubility enhancing aqueous compositionscan be carried out using traditional laboratory and safety equipmentwhen using concentrated acid and water that could generate significantheat. Within these considerations, the selection of laboratory equipmentis not critical to the formation of the solubility enhancing aqueoussolutions or compositions. More particularly, the preparation of thefirst solution wherein the reactants ammonium sulfate stock solution iscombined with sulfuric acid requires laboratory apparatuses that areapproved for heat generation, splashing and, potentially, pressurerelief. Accordingly, the first solution should be prepared in alaboratory vessel that is not sealed providing for pressure relief,rather than a potential hazardous situation with pressure build up in anunrated vessel. The ordinarily skilled artisan should be knowledgeablein the selection and use of such apparatuses.

For commercial-scale production of solubility enhancing aqueouscompositions, the ordinarily skilled artisan will recognize that thereaction between the solubilized ammonium sulfate and sulfuric acid istypically exothermic. As such, a reaction vessel appropriate to safelycontain and, typically, cool this reaction, is recommended. Commercialproduction of a first solution and a second solution can be accomplishedusing any of the teachings herein but on a larger scale than thelaboratory scale teachings and examples disclosed herein. Moreover, suchcommercial production can be accomplished, without limitation, as taughtherein or with equipment known to the ordinarily skilled artisan.

The order of adding the reactants to each other is not critical in thepreparation of a first solution. Either the stock ammonium sulfatesolution can be added to the sulfuric or, more typically, sulfuric acidis added to the stock ammonium sulfate stock solution to avoid thesplattering typical of adding a solution containing water to acid.Typically, the heat generating reaction forming the first solution ispermitted to run to conclusion, with the term “conclusion” having themeaning understood by the ordinarily skilled artisan, prior to addingthe first solution to the required water or water to the first solution,without preference to the order of addition. For the sake of clarity,conclusion of the reaction between the ammonium sulfate stock solutionand sulfuric acid typically occurs when the reactants no longer producean exothermic reaction and the temperature of the solution begins todecrease to ambient temperature.

Alternatively, the formation of a first solution is not required and theammonium sulfate stock solution and sulfuric acid can be combined withthe final desired volume of a solubility enhancing aqueous compositions.Accordingly, another aspect of the solubility enhancing aqueouscompositions provides a solubility enhancing aqueous compositioncomprising an anionic component consisting essentially of sulfate anionshaving a concentration from about 8.00 moles per liter to about 13.00moles per liter of about one-quarter of the final solubility enhancingaqueous composition volume and a cationic component consistingessentially of ammonium ions having a concentration from about 1.45moles per liter to about 2.01 moles per liter of about one-quarter ofthe final solubility enhancing aqueous composition volume or less, andwater comprising at least one-half of the final composition volume.

An alternate solubility enhancing aqueous composition comprises ananionic component comprising sulfate anions having a concentration fromabout 8.00 moles per liter to about 13.00 moles per liter about one-halfof the final solubility enhancing aqueous compositions volume and acationic component comprising ammonium ions having a concentration fromabout 1.45 moles per liter to about 2.01 moles per liter of about onehalf of the final solubility enhancing aqueous composition volume.

Another alternate solubility enhancing aqueous composition comprises ananionic component consisting essentially of sulfate anions having aconcentration from about 8.00 moles per liter to about 13.00 moles perliter and a cationic component consisting essentially of ammonium ionshaving a concentration from about 1.45 moles per liter to about 2.01moles per liter of the final solubility enhancing aqueous compositionvolume wherein said liter volume for calculation for the volume of watercomprising the ammonium ions and sulfate anions comprises at least onepercent of the total volume of the solubility enhancing aqueouscomposition.

A further alternate solubility enhancing aqueous composition comprisesan anionic component consisting essentially of sulfate anions having aconcentration from about 8.00 moles per liter to about 13.00 moles perliter of not more than about one-half of the final solubility enhancingaqueous composition volume and a cationic component consistingessentially of ammonium ions having a concentration from about 1.45moles per liter to about 2.01 moles per liter of not more than aboutone-half the final solubility enhancing aqueous composition volume.

An additional alternate solubility enhancing aqueous compositioncomprises an anionic component comprising sulfate anions having aconcentration from about 8.00 moles per liter to about 13.00 moles perliter of not more than about one-half of the final solubility enhancingaqueous composition volume and a cationic component comprising ammoniumions having a concentration from about 1.45 moles per liter to about2.01 moles per liter of not more than about one-half the finalsolubility enhancing aqueous composition volume.

Although certain aspects of the solubility enhancing aqueouscompositions allow for highly dilute concentrations for the ammoniumcations and sulfate anions, specific concentrations of these ions can becalculated on a basis as if such combination were prepared on a perliter basis wherein the volume of such preparation comprises 1%, 10%,20%, 30%, 40%, 48%, 50% or 60% of the total volume of the finalsolubility enhancing aqueous composition. For the sake of clarity, thevolume of water can be any whole number or fraction thereof in a rangefrom about 1% to about 60%. In addition, the volume of total water ineach of the solubility enhancing aqueous compositions taught herein canbe calculated by a variety of methods as taught herein and are notlimited by any one teaching. As such, the amount of water used to form asecond solution can be based on weight/weight (first solution weight tothe weight of water added to form a second solution); mass/mass (firstsolution mass to the mass of water added to form a second solution; andmass/mass (the mass of the sum of ammonium ions and sulfate ions to themass of total water in the second solution). Each of these methods canbe used in a two-step process wherein a first solution is formed andwater is added to form a second solution, or a one-step process wherethe elements of a second solution of the present invention arepre-calculated and added accordingly.

As referenced above, one aspect of the present invention provides anaqueous paper enhancing composition comprising an aqueous phasecomprising: a solubility enhancing aqueous composition wherein 1 part ofa first solution is added to about 15 to about 20 parts of water to forma second solution; sodium hydroxide solution having a concentration ofabout 5% to about 7.5% volume/volume of the total aqueous phase volumeof the composition; at least one optional surfactant selected from thegroup consisting of non-ionic surfactant and anionic surfactant having aconcentration from about 0.05 percent to about 0.15 percentvolume/volume of the total aqueous phase volume of the composition; andcopper sulfate having a concentration from about 20 percent to about 26percent mass/volume of the total aqueous phase volume of thecomposition. A further aspect of the present invention further comprisesthe addition of an acid or base to adjust the pH to a pH from about 2.5to about 3.5 to the immediately preceding composition.

A further aspect of the present invention further comprises the additionof an acid or base to adjust the pH to a pH from about 2.5 to about 3.5to the immediately preceding composition.

For the preparation of the above-referenced aqueous paper enhancingcomposition, a 20 percent to 50 percent dilute sodium hydroxide solutionis prepared using techniques well known to the skilled artisan. Therange of sodium hydroxide concentration in the present aqueous paperenhancing compositions is based on varied concentrations of sodiumhydroxide. When higher concentration sodium hydroxide solutions areused, one would typically use the lower concentration range of about0.5% volume/volume of the total aqueous element volume of thecomposition. Conversely, when lower concentration sodium hydroxidesolutions are used, one would typically use the higher concentrationrange of about 0.75% volume/volume of the total aqueous element volumeof the composition. Total aqueous element volume composition means thesum volume of the aqueous components of the present compositionincluding the solubility enhancing aqueous composition, sodium hydroxidesolution and surfactant.

Various aqueous concentrations of non-ionic and anionic surfactants arecommercially available, frequently found in concentrations of about 20%to about 80% in water. Such surfactants can also be prepared by dilutingconcentrated non-ionic surfactant and/or anionic surfactants in water todesired concentrations. Accordingly, such surfactants having aconcentration of 20%, 30%, 40%, 50%, 60%, 70% and 80% are useful in thepresent composition. Generally, surfactant concentrations of at least20% in water are useful. More particularly, a 50% concentration ofGlucopon® 420 in water (available from multiple vendors including, forexample, BASF Corp., Florham Park, N.J., USA) is useful as a nonionicsurfactant in the present aqueous paper enhancing compositions. Whenhigher concentration surfactant solutions are used, one would typicallyuse the lower concentration range of about 0.05% volume/volume of thetotal aqueous element volume of the composition. Conversely, when lowerconcentration surfactant solutions are used, one would typically use thehigher concentration range of about 0.15% volume/volume of the totalaqueous element volume of the composition.

Additionally, a solubility enhancing aqueous composition is preparedwherein 1 part of a first solution, as described above, is added toabout 15 to about 20 parts of water to form a second solution.

For preparation of the aqueous paper enhancing composition of thepresent invention, to the solubility enhancing aqueous composition isadded dilute sodium hydroxide (about 20% to about 50%) having aconcentration of about 5% to about 7.5% volume/volume of the totalaqueous element volume of the composition. The surfactant element of thepresent composition can be added to this aqueous solution or canoptionally be added following the addition of the copper sulfateelement. However, the calculation for the concentration of thesurfactant is based on the total aqueous element volume of thecomposition as if the copper sulfate had not yet been added. The atleast one surfactant is selected from the group consisting of non-ionicsurfactant and anionic surfactant having a concentration from about 0.05percent to about 0.15 percent volume/volume of the total aqueous elementvolume of the composition.

The copper sulfate element of the present aqueous paper enhancingcomposition is added to the aqueous solution described above at aconcentration from about 20 percent to about 26% mass/volume of thetotal aqueous element volume of the composition.

Once the present composition is prepared, the final pH should beadjusted to a pH of from about 2.5 to about 3.5 with a pH of about 3.0being typically used. Any base or acid can be used to increase ordecrease, respectively, the pH of such a composition. However, it isbest to utilize acids and bases already used in the presentcompositions; dilute sodium hydroxide to increase the pH and sulfuricacid to decrease the pH. Alternatively, pH is controlled throughout thevarious steps of preparation of an aqueous paper enhancing compositionof the present invention. For example, pH can be adjusted to the rangesset forth above following the addition of dilute sodium hydroxide to thepreviously prepared solubility enhancing aqueous composition, and thenagain following the addition of copper sulfate and, optionally,following the addition of copper sulfate and the anionic and/or nonionicsurfactant. As such, the pH is adjusted at least one time duringpreparation of an aqueous paper enhancing composition, typicallyfollowing the addition of the copper sulfate and/or surfactant.

The process for preparing the carbonate enhancing compositions,including aqueous carbonate enhancing compositions, can be carried outusing traditional laboratory and safety equipment when usingconcentrated acid and water that could generate significant heat. Withinthese considerations, the selection of laboratory equipment is notcritical to the formation of the carbonate enhancing compositions and/oraqueous carbonate enhancing compositions. The ordinarily skilled artisanshould be knowledgeable in the selection and use of such apparatuses.

For larger scale production batches of such carbonate enhancingcompositions of the present invention, including aqueous paper enhancingcompositions, such compositions are prepared based on the percentagestaught herein above of the elements required for preparation of suchcompositions. As a non-limiting example, such compositions can beprepared as follows: to produce 330 gallons of finished product, to anadequate-sized tank having circulation mixing, is about 2,116 pounds of17 megohm water, typically, distilled water, about 183 pounds of asolubility enhancing aqueous composition, with continued mixing, about183 pounds of 50% sodium hydroxide that is slowly added to the priormixture, with continued mixing, about 590 pounds copper sulfate, withcontinued mixing to maintain the copper sulfate in solution, and about 2pounds of 50% Glucopon® 420 UP, with continued mixing for at least aboutone hour. It is beneficial to adjust the pH after addition of eachsubsequent element beginning with the addition of the solubilityenhancing aqueous composition. pH should be adjusted to be in the rangefrom about pH 2.5 to about pH 3.5 with a median of pH 3.0 being areasonable target. Lowering the pH is accomplished by any reasonablemeans known to the skilled artisan but it is recommended to add anappropriate amount of a solubility enhancing aqueous composition; andincreasing the pH can be accomplished by any means known to the skilledartisan but is recommended to add an appropriate amount of sodiumhydroxide, particularly 50% sodium hydroxide.

The intent and benefit of the present aqueous paper enhancingcomposition, and potentially, all aqueous is to provide an aqueoussolution that is substantially free of solids. However, not all aqueouspaper enhancing compositions or carbonate enhancing compositions will befree or substantially free of solids.

Although specific embodiments have been described above, theseembodiments are not intended to limit the scope of the presentdisclosure, even where only a single embodiment is described withrespect to a particular feature. Examples of features provided in thisdisclosure are intended to be illustrative rather than restrictiveunless stated otherwise. The present disclosure is intended to coversuch alternatives, modifications and/or equivalents as would be apparentto a person skilled in the art having the benefit of this disclosure.

It is to be understood that the present compositions are limited only tothe ranges and or limitation set forth herein and not to variationswithin such ranges. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

Further modifications and alternative embodiments of various aspects ofthe embodiments described in this disclosure will be apparent to theskilled artisan in view of the present disclosure. Elements andmaterials may be substituted for those illustrated and described herein,parts and processes may be reversed, and certain features of theembodiments may be utilized independently, all as would be apparent toone skilled in the art after having the benefit of the description.Changes may be made in the elements described herein without departingfrom the spirit and scope of the appended claims.

EXAMPLES Example 1

Preparation of an ammonium sulfate stock solution for a solubilityenhancing aqueous composition: Into a volumetrically calibrated common250 mL beaker, 90 mL of deionized H₂O was added. 20 grams of (NH₄)₂SO₄was completely dissolved into the deionized water. The total volume wasbrought to 100 mL using additional deionized water. 20 grams (NH₄)₂SO₄per 100 mL H₂O is a 20% solution and is a 1.51 M solution.

Example 2

Direct preparation of a second solution for the preparation of asolubility enhancing aqueous composition without the prior preparationof a first solution wherein the ratio of a first solution equivalent towater addition in this step is four parts water to one part firstsolution equivalent:

-   -   1.15 mL of 20% (NH₄)₂SO₄ was added to a common 10 mL        polypropylene centrifuge tube    -   8.0 mL deionized water added to tube    -   0.850 mL of concentrated (95-98%) sulfuric acid (H₂SO₄) added to        tube with sufficient force to mix

Example 3

Direct preparation of a second solution for a solubility enhancingaqueous composition without the prior preparation of a first solutionwherein the ratio of a first solution equivalent to water addition inthis step is nine parts water to one part first solution equivalent:

-   -   0.576 mL of 20% (NH₄)₂SO₄ was added to a common 10 mL        polypropylene centrifuge tube    -   9.0 mL deionized water added to tube    -   0.424 mL of concentrated (95-98%) sulfuric acid (H₂SO₄) added to        tube with sufficient force to mix

Example 4

Direct preparation of a second solution for a solubility enhancingaqueous composition without the prior preparation of a first solutionwherein the ratio of a first solution equivalent to water addition inthis step is nineteen parts water to one part first solution equivalent:

-   -   0.288 mL of 20% (NH₄)₂SO₄ was added to a common 10 mL        polypropylene centrifuge tube    -   9.5 mL deionized water added to tube    -   0.212 mL of concentrated (95-98%) sulfuric acid (H₂SO₄) added to        tube with sufficient force to mix

Example 5

Preparation of solubility enhancing aqueous composition samples forliquid chromatography—mass spectrometry (LC-MS) analysis: Each ofExamples 2, 3 and 4, following addition of the sulfuric acid:

-   -   the centrifugation tubes were briefly capped and vortexed to mix        thoroughly    -   caps were loosened to vent. It was observed that the        temperatures of the centrifugation tubes were greater than        ambient temperature. Such temperature was not sufficient to melt        the centrifugation tubes.    -   reactions were allowed to run for about 60 minutes    -   after completion of the reaction time, 1 mL samples of the        reacted solutions were filtered through a 0.44 micro Pall        syringe filter and placed into labeled mass spectrometry vials    -   vials were loaded into a Thermo Q Exactive Plus MS system with a        Vanquish LC front end    -   LC Settings:    -   0.25 ml/min    -   40% methanol/60% water/0.1% formic acid    -   column temp 30° C.    -   Thermo Accucore AQ C18 polar end cap column (150 mm×3 mm)    -   Injection volumes of 20 uL    -   Low resolution parameters    -   Full MS-SIM    -   0-10 minutes    -   Positive polarity    -   Resolution: 70,000    -   AGC Target: 3×10⁶    -   Max IT: 200 ms    -   Scan Range: 50-700 mz    -   High resolution parameters    -   Full MS/dd-MS²    -   0-7 minutes    -   Positive polarity    -   Full MS: Resolution: 70,500    -   AGC Target: 3×10⁶    -   Max IT: 100 ms    -   Scan range: 50-700 mz    -   dd-MS²: Resolution: 17,500    -   AGC target: 2×10⁶    -   Max IT: 50 ms    -   Scan range: 50-700 mz    -   Minimum AGC Target: 2×10³

Example 6: Laboratory Preparations of First Solutions for Preparation ofSolubility Enhancing Aqueous Compositions for Ion ChromatographicQuantification

-   -   A 24% solution of ammonium sulfate was created by adding 96        grams of ammonium sulfate to 400 grams deionized water. The        solution was mixed to completely dissolve the ammonium sulfate.    -   Ten (10) identical 20 mL reactions were produced:        -   9.6 mL of the preceding 24% ammonium sulfate solution was            added to individually labeled common 50 mL conical tubes by            way of calibrated macropipette        -   10.4 mL of concentrated sulfuric acid (95-98% reagent grade)            was added to each tube by way of calibrated micropipette            with sufficient force to thoroughly mix        -   Tubes were allowed to stand loosely capped for an hour for            reaction to run to completion.

Example 7: Ion Chromatography (IC) Method

Samples from Example 6 were transferred to IC vials, dilutedappropriately (1:2500) to bring the ionic concentrations into the rangeof testing equipment used, and ion chromatography was undertaken usingthe following parameters:

Ion Chromatography:

Dual Thermo Dionex Aquion

Anion Side:

Column: Dionex IonPac AS22 RFIC 4×250 mm

Mobile phase: carbonate/bicarbonate buffet at 4.8/1.2 mM

Flow: 1.2 mL/min isocratic

Suppressor: Dionex ADRS 600 4 mm

Sup. Voltage: 33 mA

Standard: IC STD for sulfate, 50-500 ppm

Anion cell: 35° C.

Anion column: 30° C.

18 minute run time

Cation Side:

Column: Dionex IonPac CS16 RFIC 5×250 mm

Mobile phase: 30 mM MSA solution

Flow: 1 mL/min isocratic

Suppressor: Dionex CDRS 600 4 mm

Sup voltage: 89 mA

Standard: IC STD for ammonium 20-100 ppm

Cation cell: 40° C.

Cation column: 35° C.

18 minute run time

All 25 uL injections

Example 8. Ion Chromatography Results

Using the sample preparations set forth in Example 6 and the ionchromatography methods set forth in Example 7, the following results (10samples; 2 replicates) were obtained:

Sulfate mol/L Ammonium mol/L 9.1904799 1.6264427 8.00-13.00 1.45-2.01

Example 9: Commercial-Scale Production of a Solubility EnhancingComposition First Solution

Into a 500-gallon polyethylene conical-bottom tank was added 160.5pounds (about 19.2 gallons) of deionized water. Upon addition of thewater, a magnetic-driven shearing pump with an impeller was engaged,circulating the water in the tank. To the water was slowly added 50.7pounds of pre-weighed ammonium sulfate (GAC Chemical Corp., SearsportMaine, U.S.A.) to enable solubilization of the ammonium sulfatepreparing a 31.6% ammonium sulfate solution. The recirculating pump wasallowed to run for about 20 minutes for this batch size. Completesolubilization of the ammonium sulfate was visually confirmed bydecanting about 250 mL of solution into a PET bottle that was allowed tostand undisturbed for about 15 minutes, confirming completesolubilization.

A 50-gallon Dietrich (Corpus Christi, Texas, U.S.A.) closed-loop,stainless steel-jacketed, glass-lined reactor was pre-cooled using a CTST-230 cooling tower (Cooling Tower Systems, Macon, Georgia U.S.A.)circulating a mixture of municipal water and sufficient sodiumhypochlorite to maintain a pH from about 7.5 to about 7.8. To thisreactor was added 400.6 pounds (about 26.1 gallons) of 98% sulfuric acid(Brenntag; Henderson, Kentucky U.S.A.) while a shaft-driven paddle mixerwas engaged at 1700 rpm. To the sulfuric acid was rapidly added theammonium sulfate solution and was mixed for about 20 minutes (until thereaction mixture cooled to a temperature of about 130 degreesFahrenheit) at which time the reaction to form this first solution wascomplete.

Example 10: Commercial Production of a Solubility Enhancing CompositionSecond Solution

To a one thousand gallon polyethylene conical-bottom tank is addeddeionized water equal to the volume or mass of the first solution. Tothis water is added the first solution. The resulting mixture representsa second solution of the present invention.

Example 11: Ion Chromatography Results

Using the sample preparations set forth in Example 9 and the ionchromatography methods set forth in Example 7, the following results(averages of 3 replicates of 3 samples) were obtained:

Sulfate mol/L Ammonium mol/L 10.77769681 1.677964718

Target Ranges:

Sulfate mol/L Ammonium mol/L 8.00-13.00 1.45-2.01

Example 12. Preparation of an Aqueous Paper Enhancing Composition (AlsoUsed for the Preparation of an Aqueous Carbonate Enhancing Composition)

-   -   A 30% sodium hydroxide solution is prepared by dissolving 300        grams of sodium hydroxide per 1000 grams (1.0 L) of water;    -   A 50% Glucopon® 420 solution is prepared by dissolving 500 grams        of Glucopon 420 per 1000 grams (1.0 L) of water;    -   To an appropriate mixing vessel is added 2700.98 grams of water;    -   To the water is added 551.60 grams of a first solution (as        defined above) with slow mixing;    -   To the previous solution is added 276.91 grams of a 30% sodium        hydroxide solution with slow mixing;    -   Mix the previous solution slowly for 30 minutes and, after        which, adjust the pH to 3.0;    -   To the previous solution, slowly add 891.74 grams of copper        sulfate with mixing until the copper sulfate is fully dissolved;    -   To the previous solution, add 5.80 grams of 50% Glucopon 420 and        mix for 1 hour;    -   Adjust the final pH to 3.0 with sodium hydroxide.

Example 13. Commercial-Scale Preparation (330 Gallons of FinishedProduct) of an Aqueous Paper Enhancing Composition (Also Used for thePreparation of an Aqueous Carbonate Enhancing Composition)

-   -   To a 500 gallon polyethylene tank was added 2,116 pounds of 17        megohm water, with mixing via circulation from a roller pump;    -   To the water was added 183 pounds of a solubility enhancing        aqueous composition, with continued mixing;    -   To the prior solution was slowly added 183 pounds of 50% sodium        hydroxide, with continued mixing;    -   To the prior solution was added 590 pounds of copper sulfate,        with continued mixing to maintain the copper sulfate in        solution;    -   To the prior solution/suspension was added 2 pounds of Glucopon        420® with continued mixing for one hour    -   pH of the final solution is adjusted to a pH from about 2.5 to        about 3.5 using additional solubility enhancing aqueous        composition in the pH needs to be lowered or add sodium        hydroxide if the pH needs to be increased to the target range.

1. A paper forming mixture comprising a paper making fiber and at leastone carbonate enhanced composition wherein the at least one carbonateenhanced composition comprises: a carbonate selected from the groupconsisting of at least one calcium carbonate, at least one silvercarbonate, at least one organic compound carbonate and mixtures thereof;and at least one carbonate enhancing composition wherein the carbonateenhancing composition comprises: a solubility enhancing aqueouscomposition comprising an anionic component consisting essentially ofsulfate ions, alone or in combination with bisulfate ions, having aconcentration from about 8.00 moles per liter to about 13.00 moles perliter of the composition volume; a cationic component consistingessentially of ammonium ions having a concentration from about 1.45moles per liter to about 2.01 moles per liter of the composition volume;and hydrogen ions in a concentration from about 17.38 mols per liter toabout 21.68 moles per liter of the composition volume; sodium hydroxidesolution having a concentration of about 5% to about 7.5% volume/volumeof the total aqueous phase volume of the composition; and a sulfateselected from the group consisting of copper sulfate, silver sulfate andcombinations thereof having a concentration from about 20 percent toabout 26 percent mass/volume of the total aqueous phase volume of thecomposition.
 2. A paper forming mixture of claim 1, wherein the papermaking fiber is pulp wood.
 3. A method of increasing at least one of thegroup consisting of paper tensile, bond and burst strength of papercomprising the addition of at least one carbonate enhanced compositionto the wet-end of a paper making process compared to an equal amount ofunenhanced calcium carbonate.
 4. Antimicrobial paper comprising paperprepared by the addition of at least one carbonate enhanced compositionto the wet-end of a paper making process.
 5. A paper enhancingcomposition comprising water, at least one solubility enhancing aqueouscomposition, sodium hydroxide, and copper sulfate
 6. A paper enhancingcomposition of claim 5, further comprising at least one surfactantselected from the group consisting of at least one non-ionic surfactantsand at least one anionic surfactant.
 7. A paper enhancing composition ofclaim 6, wherein the solubility enhancing aqueous composition comprises1 part of a first solution added to about 15 to about 20 parts of waterto form a second solution; sodium hydroxide solution having aconcentration of about 5% to about 7.5% volume/volume of the totalaqueous phase volume of the composition; and copper sulfate having aconcentration from about 20 percent to about 26 percent mass/volume ofthe total aqueous phase volume of the composition.
 8. A paper enhancingcomposition of claim 7, further comprising the addition of an acid orbase to adjust the pH to a pH from about 2.5 to about 3.5.
 9. Enhancedpaper comprising paper having applied during the wet press stage ofpaper production at least one aqueous enhancing paper composition.
 10. Amethod of preparing paper for medical and industrial protective usescomprising applying at least one aqueous paper enhancing composition atany stage during the paper making process.
 11. A paper coatingcomprising at least one aqueous paper enhancing composition.
 12. Paperused for medical and industrial protective purposes comprising papercoated with at least one paper enhancing composition.
 13. Coated paperhaving antimicrobial activity comprising paper coated with at least onepaper enhancing composition.
 14. Coated paper of claim 13, wherein theantimicrobial activity is selected from the group consisting ofantibacterial, antifungal, antiviral and anti-mold.
 15. A method ofextending the shelf-life of perishable foodstuff comprising placing suchfoodstuff in contact with coated paper of claim
 11. 16. Antimicrobialpaper comprising paper prepared by the addition of at least one paperenhancing composition added to paper in the wet-end stage of the papermaking process, applied to paper during the wet press stage of the papermaking process or applied to paper or paper products as a coating.17-18. (canceled)
 19. A paper forming mixture of claim 1, wherein theaqueous carbonate enhancing composition further comprises at least onesurfactant selected from the group consisting of non-ionic surfactantsand anionic surfactants having a concentration from about 0.05 percentto about 0.15 percent volume/volume of the total aqueous phase volume ofthe composition.
 20. A paper forming mixture composition of claim 1,wherein the aqueous carbonate enhancing composition further comprises atleast one acid or at least one base to adjust the final pH in the rangefrom about 2.5 to about 3.5.
 21. A paper forming mixture of claim 20,wherein the paper making fiber is pulp wood.
 22. A paper forming mixturecomposition of claim 19, wherein the aqueous carbonate enhancingcomposition further comprises at least one acid or at least one base toadjust the final pH in the range from about 2.5 to about 3.5.
 23. Apaper forming mixture consisting essentially of a paper making fiber andat least one carbonate enhanced composition wherein the at least onecarbonate enhanced composition consisting essentially of: A carbonateselected from the group consisting of at least one calcium carbonate, atleast one silver carbonate, at least one organic compound carbonate andmixtures thereof; and at least one carbonate enhancing compositionwherein the carbonate enhancing composition is consisting essentiallyof: a solubility enhancing aqueous composition consisting essentially ofan anionic component consisting essentially of sulfate ions, alone or incombination with bisulfate ions, having a concentration from about 8.00moles per liter to about 13.00 moles per liter of the compositionvolume; a cationic component consisting essentially of ammonium ionshaving a concentration from about 1.45 moles per liter to about 2.01moles per liter of the composition volume; and hydrogen ions in aconcentration from about 17.38 mols per liter to about 21.68 moles perliter of the composition volume; sodium hydroxide solution having aconcentration of about 5% to about 7.5% volume/volume of the totalaqueous phase volume of the composition; and a sulfate selected from thegroup consisting of copper sulfate, silver sulfate and combinationsthereof having a concentration from about 20 percent to about 26 percentmass/volume of the total aqueous phase volume of the composition.
 24. Apaper forming mixture of claim 23, wherein the paper making fiber ispulp wood.
 25. A paper forming mixture composition of claim 23, whereinthe aqueous carbonate enhancing composition further consists of at leastone acid or at least one base to adjust the final pH in the range fromabout 2.5 to about 3.5.
 26. A paper forming mixture of claim 23, whereinthe aqueous carbonate enhancing composition further consists at of atleast one surfactant selected from the group consisting of non-ionicsurfactants and anionic surfactants having a concentration from about0.05 percent to about 0.15 percent volume/volume of the total aqueousphase volume of the composition.
 27. A paper forming mixture compositionof claim 26, wherein the aqueous carbonate enhancing composition furtherconsists of at least one acid or at least one base to adjust the finalpH in the range from about 2.5 to about 3.5.
 28. A paper forming mixtureof claim 26, wherein the paper making fiber is pulp wood.
 29. A paperforming mixture of claim 22, wherein the carbonate enhancing compositionis substantially free of solids.
 30. A paper forming mixture of claim27, wherein the carbonate enhancing composition is substantially free ofsolids.